JPH0764962B2 - Heat-resistant conductive adhesive resin composition - Google Patents

Heat-resistant conductive adhesive resin composition

Info

Publication number
JPH0764962B2
JPH0764962B2 JP28890186A JP28890186A JPH0764962B2 JP H0764962 B2 JPH0764962 B2 JP H0764962B2 JP 28890186 A JP28890186 A JP 28890186A JP 28890186 A JP28890186 A JP 28890186A JP H0764962 B2 JPH0764962 B2 JP H0764962B2
Authority
JP
Japan
Prior art keywords
acid
density polyethylene
low
graft
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP28890186A
Other languages
Japanese (ja)
Other versions
JPS63142050A (en
Inventor
朝信 近藤
正夫 岡村
Original Assignee
日本ユニカ−株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ユニカ−株式会社 filed Critical 日本ユニカ−株式会社
Priority to JP28890186A priority Critical patent/JPH0764962B2/en
Publication of JPS63142050A publication Critical patent/JPS63142050A/en
Priority to US07/353,598 priority patent/US5176852A/en
Publication of JPH0764962B2 publication Critical patent/JPH0764962B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2418—Coating or impregnation increases electrical conductivity or anti-static quality
    • Y10T442/2426—Elemental carbon containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2738—Coating or impregnation intended to function as an adhesive to solid surfaces subsequently associated therewith

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電線関係の用途、コンピユータ関係の用途、家
電関係の用途、プラスチツク関係の用途、ゴム関係の用
途、無機材関係の用途等に於て、広範囲に利用される成
形加工性が容易で、かつ低温接着性に優れた耐熱導電性
接着性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is applicable to electric wires, computers, home appliances, plastics, rubber, inorganic materials, and the like. Thus, the present invention relates to a heat-resistant conductive adhesive resin composition which is widely used and has easy moldability and excellent low-temperature adhesiveness.

〔従来の技術〕[Conventional technology]

従来より、この種の導電性接着性樹脂組成物としては、
各種ポリオレフイン系樹脂やその他塩ビ系樹脂等に接着
性を付与し、これにカーボンブラツクや黒鉛等導電性を
有する固体粉末を混練りしたものが知られている。例え
ば低密度ポリエチレンに無水マレイン酸をグラフトさせ
ることによつて接着性を付与し、これにカーボンブラツ
クを混練りしたもの（特開昭58-53935号公報）が提案さ
れている。Conventionally, as this kind of conductive adhesive resin composition,
It is known that various polyolefin resins, other vinyl chloride resins, and the like are provided with adhesiveness, and conductive solid powders such as carbon black and graphite are kneaded. For example, it has been proposed that low-density polyethylene is grafted with maleic anhydride to impart adhesiveness, and carbon black is kneaded with this (JP-A-58-53935).

しかしながら、これら従来技術においては、前記産業分
野において進行している高度な導電性樹脂に対する要求
レベルを満足させることは困難である。即ち、接着剤や
溶剤等を使用せずに相手の基材に高い接着性を有するこ
と、かつ耐熱性、耐温水性、耐寒性等接着耐久性を有す
ること、比較的低温で接着が可能であること、及びフイ
ルム加工等加工性が容易であることが要求項目としてあ
げられる。However, in these conventional techniques, it is difficult to satisfy the required level for the highly conductive resin which is being advanced in the industrial field. That is, it has high adhesiveness to the base material of the other party without using an adhesive or solvent, and has adhesive durability such as heat resistance, hot water resistance, and cold resistance, and can be adhered at a relatively low temperature. There is a requirement that the workability is easy and the workability such as film processing is easy.

低密度ポリエチレンを使用すると、充分な接着性が得ら
れず、耐熱性が低く、前記産業分野において要求特性を
満足し得ない事例が多い。高密度ポリエチレンの場合
は、導電材の高充填性が充分でなく、所定の導電性を得
るため、粉末導電性物質の量を増加するとその後のフイ
ルム加工が困難となる。また、接着力も低下し特に低温
接着性が得られづらい。塩化ビニル樹脂が使用される場
合もあるが、接着性付与が困難であり、新たに接着剤を
必要とする。ナイロン等エンジニアリング樹脂を使用す
るケースも見られるが、他特性はある程度犠牲にし、耐
熱性を強く要求される場合の様に特殊な使用が限られ
る。When low-density polyethylene is used, sufficient adhesiveness cannot be obtained, heat resistance is low, and in many cases, the required properties cannot be satisfied in the industrial field. In the case of high-density polyethylene, the high filling property of the conductive material is not sufficient and a predetermined conductivity is obtained. Therefore, if the amount of the powder conductive material is increased, the subsequent film processing becomes difficult. In addition, the adhesive strength is also reduced, and it is difficult to obtain low-temperature adhesiveness. Vinyl chloride resin is sometimes used, but it is difficult to impart adhesiveness and a new adhesive is required. There are cases where engineering resins such as nylon are used, but other properties are sacrificed to some extent, and special use is limited as in cases where heat resistance is strongly required.

〔本発明が解決しようとする問題点〕[Problems to be Solved by the Present Invention]

本発明は問題となつている次の各項を解決しようという
ものである。The present invention is intended to solve the following problems that are at issue.

１） 接着性が不十分であるための問題点。1) Problems due to insufficient adhesion.

２） 高温下での接着力不十分であるための問題点。2) Problems due to insufficient adhesive strength at high temperatures.

３） 耐熱接着性に優れている既存素材はあるが低温で
の接着性に劣る。3) There are existing materials with excellent heat resistant adhesiveness, but poor adhesiveness at low temperatures.

４） 接着試験片を温水中に長期に浸漬すると接着力が
低下することによる問題点。4) The problem that the adhesive strength decreases when the adhesion test piece is immersed in warm water for a long time.

５） 良導電性を得るために導電剤を添加すると接着性
や加工性の大幅な低下による問題点。5) When a conductive agent is added to obtain good conductivity, there is a problem that adhesiveness and workability are significantly reduced.

６） フイルム加工、ラミネート加工の容易な素材が少
ない。6) There are few materials that are easy to film and laminate.

〔問題点を解決するための手段〕[Means for solving problems]

本発明はかゝる観点にたつて創案されたものであつて、
単に導電性に優れているのみならず、直鎖状低密度ポリ
エチレンを使用することによつて前記問題点の解決を計
り、各分野の高度な要求に応え得ることを発見した。The present invention was devised from this point of view,
It has been found that not only is it excellent in conductivity, but the use of linear low-density polyethylene solves the above-mentioned problems and can meet the high demands in each field.

また、直鎖状低密度ポリエチレンを使用することにより
エチレン−エチルアクリレート共重合体、エチレン−酢
酸ビニル共重合体、無極性ポリオレフイン系低結晶性樹
脂等他樹脂との相溶性が良く、更にこれらを混練りする
ことによつて、直鎖状低密度ポリエチレンの諸特性を維
持し、柔軟性、衝撃強度等の特性を更に高めることが可
能であることを発見した。Further, by using linear low density polyethylene, the compatibility with other resins such as ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, non-polar polyolefin low crystalline resin is good, and further these It was discovered that by kneading, various properties of linear low-density polyethylene can be maintained and the properties such as flexibility and impact strength can be further enhanced.

従つて、本発明の主題は、 （ａ） 下記の混合物 （ｉ） 不飽和有機酸類若しくはそれらの酸無水物、酸
ハロゲン化物、酸アミド若しくは酸イミドで又は不飽和
エポキシ化合物類でグラフト変性された直鎖状低密度ポ
リエチレンと不飽和有機酸類若しくはそれらの酸無水
物、酸ハロゲン化物、酸アミド若しくは酸イミドで又は
不飽和エポキシ化合物類でグラフト変性されたエチレン
−エチレン性不飽和基含有エステル共重合体との混合
物、及び （ii） 上記グラフト変性された直鎖状低密度ポリエチ
レンと不飽和有機酸類若しくはそれらの酸無水物、酸ハ
ロゲン化物、酸アミド若しくは酸イミドで又は不飽和エ
ポキシ化合物類でグラフト変性された無極性ポリオレフ
ィン系低結晶性樹脂との混合物 から選択されたグラフト変性物50〜95重量％と、 （ｂ） 粉末導電性物質50〜５重量％ とから成ることを特徴とする成形加工が容易でかつ低温
接着性に優れた耐熱導電性接着性樹脂組成物にある。The subject of the invention is therefore the following: (a) the following mixtures: (i) graft-modified with unsaturated organic acids or their anhydrides, acid halides, acid amides or acid imides or with unsaturated epoxy compounds. Ethylene-ethylenically unsaturated group-containing ester copolymer graft-modified with linear low-density polyethylene and unsaturated organic acids or their acid anhydrides, acid halides, acid amides or acid imides or with unsaturated epoxy compounds (Ii) graft-modified linear low-density polyethylene with unsaturated organic acids or their acid anhydrides, acid halides, acid amides or acid imides or unsaturated epoxy compounds 50-95% by weight of a graft modified product selected from a mixture with a modified non-polar polyolefin low crystallinity resin, (B) A heat-resistant conductive adhesive resin composition characterized by comprising 50 to 5% by weight of a powdery conductive material, which is easy to mold and has excellent low-temperature adhesiveness.

従つて、本発明の基となる樹脂は要求性能に応えて直鎖
状低密度ポリエチレンとエチレン−エチレン性不飽和基
含有エステル共重合体又は無極性ポリオレフイン系低結
晶性樹脂から成る組成系であり、前記基本的な問題点を
解決し得ることを発見した。直鎖状低密度ポリエチレン
に他樹脂を混練りすることによつて更に向上する諸特性
の概要は次の通りである。（１）広範囲に柔軟度を有す
る製品、例えばフイルム製品を得ることが出来る。
（２）導電材の練り込みに当たり、次の工程であるフイ
ルム加工、ラミネート加工等で良好な加工性を失わずに
その充填量を増加させることが可能である（相溶性が悪
く、均一混合が得られなかつた場合は、加工、特にフイ
ルム加工、ラミネート加工時に膜切れ等重大な支障を来
すことゝなる）。（３）耐寒性、耐衝撃性を更に高める
ことができる、等。Therefore, the resin as the base of the present invention is a composition system consisting of linear low-density polyethylene and an ethylene-ethylenically unsaturated group-containing ester copolymer or a non-polar polyolefin low-crystalline resin in response to the required performance. Have found that the above basic problems can be solved. The outline of various characteristics further improved by kneading the linear low-density polyethylene with another resin is as follows. (1) It is possible to obtain a product having a wide range of flexibility, for example, a film product.
(2) In kneading the conductive material, it is possible to increase the filling amount without losing good workability in the next step such as film processing and laminating processing (poor compatibility and uniform mixing). If it is not obtained, it will cause serious troubles such as film breakage during processing, especially film processing and laminating processing). (3) Cold resistance and impact resistance can be further improved.

接着手段としては、相手の基材に接着性をもたせる方法
或るいは塩化ビニルのフイルム等でよく見られる接着剤
を塗布する方法があるが、ここでは本発明の樹脂自身に
接着機能を付与すること、かつ導電材の充填量を増加し
ても接着強度の低下を極力小さくすることを前提として
開発を行つた。更には、プラスチツクを相手基材とし、
フイルム加工する場合、共押出も可能であると同時に、
後貼合も可能であることを前提としている。すなわち、
接着剤や溶剤等の手段を得ずして、種々の基材に接着力
を有する素材の開発に関するものである。As the adhesion means, there is a method of providing an adhesive property to a mating base material, or a method of applying an adhesive which is often found in a film of vinyl chloride, etc., but here, the resin of the present invention is provided with an adhesion function. In addition, the development was carried out on the premise that the decrease in adhesive strength is minimized even if the filling amount of the conductive material is increased. Furthermore, using plastic as the base material,
When film processing, co-extrusion is also possible,
It is premised that post-bonding is possible. That is,
The present invention relates to the development of a material having an adhesive force to various base materials without obtaining a means such as an adhesive or a solvent.

本発明は、以上のごとく、加工性、特にフイルム加工
性、ラミネート加工が容易で、良導電性、高い接着性及
びその耐熱性、耐久性の優れた樹脂に関するものであ
る。INDUSTRIAL APPLICABILITY As described above, the present invention relates to a resin which is excellent in processability, particularly film processability and laminating, and which has excellent conductivity, high adhesiveness, heat resistance and durability.

本樹脂の製造法の概要を述べると、（１）基樹脂への接
着性付与及び、（２）本樹脂に導電性を付与する、の二
工程からなる。The outline of the production method of the present resin is composed of two steps of (1) imparting adhesiveness to the base resin and (2) imparting conductivity to the present resin.

（１）の工程で従来から存在する或るいは考えられる樹
脂によつては得られにくい良好なレベルの接着性や、フ
イルム加工性及び耐熱性が決まる。本発明は、直鎖状低
密度ポリエチレンを基樹脂とすることにより、耐熱性、
機械的特性、耐摩耗性、耐疲労性、製膜製の良好な製品
が得られることを見いだした。更に特記すべきことは接
着性付与が容易でありかつ、金属を始め多くの被着体に
高度なレベルで接着性を有することが分かつた。同時に
実使用時の接着力の耐久性、即ち、耐熱性、耐温水性、
耐寒性、耐疲労性等も良く、安定していることが明かと
なつた。これらの特徴は従来の高圧法低密度ポリエチレ
ン或るいは高密度ポリエチレンでは得られなかつたこと
である。In the step (1), a good level of adhesiveness, film processability and heat resistance, which are difficult to obtain with conventional resins existing or considered, are determined. The present invention, by using a linear low-density polyethylene as a base resin, heat resistance,
It has been found that a good product having mechanical properties, wear resistance, fatigue resistance, and film formation can be obtained. Further, it should be noted that the adhesiveness can be easily imparted and the adhesiveness to a large number of adherends including metal can be obtained at a high level. At the same time, the durability of the adhesive strength during actual use, that is, heat resistance, warm water resistance,
It was revealed that it was stable with good cold resistance and fatigue resistance. These characteristics are not available in conventional high-pressure low-density polyethylene or high-density polyethylene.

一方、高い接着耐熱性を維持しつゝ、より低温で接着可
能であることを要請されるケースも多い。これは前に述
べた接着剤や溶剤等を使用せずに接着させる事を前提と
しているため、相溶性に優れている直鎖状低密度ポリエ
チレンを使用し、融点の低いエチレン−エチレンアクリ
レート共重合体、エチレン−酢酸ビニル共重合体、無極
性ポリオレフイン系低結晶性樹脂等を混練りし、接着性
を付与することによつて解決を計つた。相溶性が悪く、
不均一混合の場合は、諸特性の中で特にフイルム加工を
困難にすることは前に述べた通りである。他方、これら
低融点の樹脂を混練りしても直鎖状低密度ポリエチレン
の有する諸特性をほゞ元のレベルに維持する技術、或い
は要求特性によつて更に向上させる技術を確立した。エ
チレン−エチルアクリレート共重合体、エチレン−酢酸
ビニル共重合体、無極性ポリオレフイン系低結晶性樹脂
等はいずれも目的とする効果が得られた。エチレン−エ
チルアクリレート共重合体、エチレン−酢酸ビニル共重
合体の場合、その共重合モノマーの含有量によつて異な
るが接着温度を10-25℃低下させることができ、耐熱接
着性を保つた上で低温接着性を可能とした。その際の、
直鎖状低密度ポリエチレンに対する混合比は、０−70重
量％、好ましくは25-60重量％である。On the other hand, there are many cases in which it is required to be able to bond at a lower temperature while maintaining high bonding heat resistance. Since this is premised on bonding without using the adhesive or solvent mentioned above, linear low density polyethylene with excellent compatibility is used, and ethylene-ethylene acrylate copolymer with a low melting point is used. The solution was made by kneading a coalesced product, an ethylene-vinyl acetate copolymer, a nonpolar polyolefin low-crystalline resin and the like to impart adhesiveness. Poor compatibility,
As described above, in the case of non-uniform mixing, film processing is particularly difficult among the various properties. On the other hand, a technique has been established for maintaining various properties of linear low-density polyethylene at a substantially original level even if these low melting point resins are kneaded, or a technique for further improving the properties depending on required properties. The ethylene-ethyl acrylate copolymer, the ethylene-vinyl acetate copolymer, the non-polar polyolefin low crystallinity resin and the like all had the desired effects. In the case of ethylene-ethyl acrylate copolymer and ethylene-vinyl acetate copolymer, the adhesion temperature can be lowered by 10-25 ° C depending on the content of the copolymerization monomer, and the heat-resistant adhesive property can be maintained. It enables low temperature adhesion. At that time,
The mixing ratio with respect to the linear low density polyethylene is 0-70% by weight, preferably 25-60% by weight.

引き続き、直鎖状低密度ポリエチレンとエチレン−エチ
レン性不飽和基含有エチレン共重合体又は無極性ポリオ
レフイン系低結晶性樹脂との混合物に接着性を付与すう
工程について述べる。本工程は有機過酸化物の存在化で
不飽和有機酸又はその誘導体或いは不飽和エポキシ化合
物等を前記樹脂組成物にグラフト反応させるものであ
る。具体的に述べると、前記樹脂組成物と有機過酸化物
とグラフト剤を均一に混合し、押出機又はニーダー等で
加熱混合し、同時にグラフト反応を完結させるものであ
る。混合が不均一の場合、ゲルの発生、接着性の不均
一、接着耐久性の低下、特に耐温水性の低下を来しやす
いので注意を要する。加熱混合も使用機械の仕様、例え
ば、押出機のスクリユー形状等、仕込みからグラフト反
応完結までの温度プロフアイル等の検討を怠ると、不均
一混合の場合と同様に品質が不安定となる。本最終製品
としてフイルム状を考えている場合は、ゲル発生防止技
術の確立は重要でありかつ不可欠である。また、反応不
十分の場合、前記接着耐久性に問題を生じるばかりでな
く、フイルム加工時の目ヤニ発生の一因ともなる。Next, the step of imparting adhesiveness to a mixture of linear low-density polyethylene and an ethylene-ethylenically unsaturated group-containing ethylene copolymer or nonpolar polyolefin-based low crystalline resin will be described. In this step, an unsaturated organic acid or its derivative or an unsaturated epoxy compound or the like is graft-reacted with the resin composition in the presence of an organic peroxide. Specifically, the resin composition, the organic peroxide, and the grafting agent are uniformly mixed and heated and mixed with an extruder or a kneader, and at the same time, the grafting reaction is completed. If the mixing is non-uniform, care should be taken because gelation, non-uniform adhesion, decrease in adhesion durability, especially decrease in hot water resistance are likely to occur. In the case of heat mixing, if the specifications of the machine used, for example, the screw shape of the extruder and the temperature profile from the charging to the completion of the graft reaction are neglected, the quality becomes unstable as in the case of non-uniform mixing. When a film-like product is considered as the final product, establishment of gel generation prevention technology is important and indispensable. In addition, if the reaction is insufficient, not only does the adhesion durability become a problem, but it also causes the occurrence of eye blemishes during film processing.

上記のグラフト反応を例えば直鎖状低密度ポリエチレン
とエチレン−エチレン性不飽和基含有エステル共重合体
との混合物について行えば、前記の樹脂混合物（ｉ）、
即ち、グラフト変性された直鎖状低密度ポリエチレンと
グラフト変性されたエチレン−エチレン性不飽和基含有
エステル共重合体との混合物が得られる。また、直鎖状
低密度ポリエチレンと無極性ポリオレフィン系低結晶性
樹脂との混合物について上記のグラフト反応を行えば、
前記の樹脂混合物（ii）、即ち、グラフト変性された直
鎖状低密度ポリエチレンとグラフト変性された無極性ポ
リオレフィン系低結晶性樹脂との混合物が得られる。When the above graft reaction is carried out, for example, on a mixture of linear low density polyethylene and an ethylene-ethylenically unsaturated group-containing ester copolymer, the above resin mixture (i),
That is, a mixture of the graft-modified linear low-density polyethylene and the graft-modified ethylene-ethylenically unsaturated group-containing ester copolymer is obtained. Further, if the above graft reaction is performed on a mixture of linear low-density polyethylene and non-polar polyolefin low-crystalline resin,
The above resin mixture (ii), that is, a mixture of the graft-modified linear low-density polyethylene and the graft-modified non-polar polyolefin low-crystalline resin is obtained.

なお、接着性を付与する工程において、次のような手段
についても検討を行つたが、両者とも同様な結果が得ら
れた。基樹脂が直鎖状低密度ポリエチレンとエチレン−
エチルアクリレート共重合体若しくはエチレン−酢酸ビ
ニル共重合体又は無極性ポリオレフイン系低結晶性樹脂
との混合系の場合、（１）各々別個にグラフト処理を行
つた後、混合する、（２）有機過酸化物とグラフト剤を
別々に樹脂と均一混合し、更に加熱混練りした場合もふ
くめ、その後両者を加熱混合する、の両ケースである。In addition, in the step of imparting the adhesiveness, the following means were also examined, but the same result was obtained in both cases. Base resin is linear low density polyethylene and ethylene-
In the case of a mixed system with an ethyl acrylate copolymer, an ethylene-vinyl acetate copolymer, or a non-polar polyolefin-based low crystalline resin, (1) each is individually grafted and then mixed, (2) an organic peroxide. In both cases, the oxide and the grafting agent are separately and uniformly mixed with the resin, and when the mixture is further kneaded by heating, the two are heated and mixed.

引き続き、導電性付与のための導電材混練り工程につい
て述べる。導電材の混合方式には、予め、高濃度のマス
ターバツチを作つておき、所定の濃度に希釈する方法
と、直接所定の組成に混合する方式とがある。一長一短
があるが、何れの方式でも同等の品質の物が得られた。
混練り機も押出機、ニーダー、ロール等何れでもよい
が、導電材の飛散を防ぐために密閉型のニーダーが好ま
しい。不均一混合の場合は、導電性や加工性等に問題が
生じる。従つて均一混練りは不可欠な条件となる。しか
し、均一混合を意識するあまり、過剰混練りとなると、
導電材の種類によつては、導電特性が低下することがあ
る。混練りに際しては、必要に応じて酸化安定剤、分散
剤、難燃材等を添加することがある。多くの導電材は吸
湿性が高く、防湿管理或るいは使用に先立つて乾燥する
必要がある。Next, the conductive material kneading step for imparting conductivity will be described. As the mixing method of the conductive material, there are a method of preparing a high-concentration master batch in advance and diluting it to a predetermined concentration, and a method of directly mixing it to a predetermined composition. Although there are merits and demerits, products of equivalent quality were obtained by either method.
The kneader may be an extruder, a kneader, a roll, or the like, but a closed kneader is preferable in order to prevent the conductive material from scattering. In the case of non-uniform mixing, problems occur in conductivity and workability. Therefore, uniform kneading is an essential condition. However, if you become over-kneaded because you are conscious of uniform mixing,
Depending on the type of conductive material, the conductive characteristics may be degraded. When kneading, an oxidation stabilizer, a dispersant, a flame retardant, etc. may be added if necessary. Many electrically conductive materials are highly hygroscopic and require moisture control or drying prior to use.

本発明の組成物における直鎖状低密度ポリエチレンは、
有機金属触媒を用いて低圧法によつて得られたエチレン
−α−オレフイン共重合物であり、他に第三成分を少量
含んでもよい。密度は、α−オレフインの含量によつて
調節され、一般にはα−オレフイン５−15重量％、密度
0.91-0.94の範囲である。α−オレフインとしては炭素
原子数３−８個のものが好適であり、例えばプロピレ
ン、ブテン、ヘキセン、ペンテン、４−メチルペンテン
等を挙げることが出来る。有機金属触媒としては、チー
グラー型、フイリツプス型等が代表例として挙げられ
る。重合系としては溶液法、気相法等である。直鎖状低
密度ポリエチレンは気相法で得られたものが好ましく、
その製法には例えば、米国ユニオンカーバイド社の特許
特公昭61-363号公報、特開昭59-230006号公報等をあげ
ることができる。メルトインデツクス（JIS K−6760に
よつて測定し、g/10分の値で示す。以下MIと略す）とし
ては0.5-50の範囲が好ましい。MI0.5以下の物を用いる
と、得られたグラフト変成物のMIの低下が著しく、成形
加工性が非常に悪くなる。一方、MIが50以上になると溶
融時の粘度が低く成り過ぎ、グラフト変成工程、成形加
工性に困難が生ずる。The linear low density polyethylene in the composition of the present invention is
It is an ethylene-α-olefin copolymer obtained by a low pressure method using an organometallic catalyst, and may further contain a small amount of a third component. Density is regulated by the content of α-olefin, generally 5-15% by weight of α-olefin, density
The range is 0.91-0.94. As the α-olefin, those having 3 to 8 carbon atoms are preferable, and examples thereof include propylene, butene, hexene, pentene, and 4-methylpentene. Typical examples of the organometallic catalyst include a Ziegler type and a Phillips type. Examples of the polymerization system include a solution method and a gas phase method. The linear low density polyethylene is preferably obtained by a gas phase method,
Examples of the manufacturing method include Japanese Patent Publication No. 61-363 and Japanese Patent Publication No. 59-230006 of Union Carbide Corporation in the United States. The melt index (measured according to JIS K-6760 and expressed as a value in g / 10 minutes; hereinafter abbreviated as MI) is preferably in the range of 0.5-50. If the MI of 0.5 or less is used, the MI of the obtained graft modified product is remarkably lowered, and the moldability is extremely deteriorated. On the other hand, when the MI is 50 or more, the viscosity at the time of melting becomes too low, which causes difficulty in the graft modification process and molding processability.

直鎖状低密度ポリエチレンは重量平均分子量（Mw）と数
平均分子量（Mn）との比Mw/Mnが2.5−４である分子量分
布の狭いものが更に好ましい。The linear low-density polyethylene is more preferably a narrow molecular weight distribution having a ratio Mw / Mn of weight average molecular weight (Mw) to number average molecular weight (Mn) of 2.5-4.

本発明の他の主要成分であるエチレン−エチレン性不飽
和基含有エステル共重合体としては、エチレン−アクリ
ル酸エチル共重合体、エチレン−メタクリル酸メチル共
重合体等のエチレン−不飽和カルボン酸エステル共重合
体、及びエチレン−酢酸ビニル共重合体、エチレン−プ
ロピオン酸ビニル共重合体等のエチレン−カルボン酸ビ
ニルエステル共重合体等を挙げることが出来るが、この
中で特に好ましいのはエチレン−アクリル酸エチル共重
合体又はエチレン−酢酸ビニル共重合体である。エチレ
ン−エチレン性不飽和基含有エステル共重合体は、MIが
0.1-200のものが使用できるが、好ましくは0.5-30の範
囲である。共重合体中のエステル単量体含量は40重量％
以下が好ましく、特に５−25重量％のものが好ましい。
他の主要成分として無極性ポリオレフイン系低結晶性樹
脂を使用しても良い。無極性ポリオレフイン系低結晶性
樹脂としては米国ユニオンカーバイド社製の超低密度ポ
リエチレン（密度0.91以下）を例示できる。Examples of the ethylene-ethylenically unsaturated group-containing ester copolymer, which is another main component of the present invention, include ethylene-unsaturated carboxylic acid esters such as ethylene-ethyl acrylate copolymer and ethylene-methyl methacrylate copolymer. Examples thereof include copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl propionate copolymers and other ethylene-carboxylic acid vinyl ester copolymers. Of these, ethylene-acrylic is particularly preferred. It is an ethyl acid copolymer or an ethylene-vinyl acetate copolymer. The ethylene-ethylenically unsaturated group-containing ester copolymer has MI
Although 0.1-200 can be used, it is preferably in the range of 0.5-30. The content of ester monomer in the copolymer is 40% by weight
The following is preferable, and 5 to 25% by weight is particularly preferable.
A non-polar polyolefin type low crystalline resin may be used as the other main component. Examples of the non-polar polyolefin low crystallinity resin include ultra low density polyethylene (density 0.91 or less) manufactured by Union Carbide Co., USA.

直鎖状低密度ポリエチレンとエチレン−エチレン性不飽
和基含有エステル共重合体又は無極性ポリオレフイン系
低結晶性樹脂の混合物にグラフト重合される不飽和有機
酸類としてはフマール酸、アクリル酸、イタコン酸、ハ
イミツク酸、マレイン酸、無水マレイン酸等が挙げら
れ、また、これらの酸ハロゲン化物、酸エステル、酸ア
ミド、酸イミド等も有用である。さらに、グリシジルメ
タクリレート等の不飽和エポキシ化合物類も有用であ
る。中でも無水マレイン酸を使用することによつて、高
度でかつ安定した接着性を得ることを見いだした。As the unsaturated organic acids graft-polymerized to a mixture of linear low-density polyethylene and ethylene-ethylenically unsaturated group-containing ester copolymer or apolar polyolefin low crystalline resin, fumaric acid, acrylic acid, itaconic acid, Examples thereof include hymic acid, maleic acid, maleic anhydride, etc., and their acid halides, acid esters, acid amides, acid imides, etc. are also useful. Further, unsaturated epoxy compounds such as glycidyl methacrylate are also useful. Among them, it has been found that by using maleic anhydride, high and stable adhesion can be obtained.

直鎖状低密度ポリエチレンとエチレン−エチレン性不飽
和基含有エステル共重合体又は無極性ポリオレフイン系
低結晶性樹脂の混合物にグラフト重合される無水マレイ
ン酸の配合量は0.05-5.0重量％の範囲であり、特に好ま
しい範囲は0.1-2.0重量％である。無水マレイン酸の配
合量が、0.05重量％未満では接着性の向上が僅かであ
り、一方、5.0重量％以上の場合には接着力の向上が頭
打ちとなるだけでなくゲルの発生が見られる等他の特性
が低下する。グラフト重合反応させるためには、温度条
件を適当に選べばラジカル開始剤が存在しない状態でも
重合反応は進行するが、存在する方が好ましい。ラヂカ
ル開始剤としては、ジアルキルパーオキサイド、パーオ
キシケタール類が適当である。なお、添加量が微量であ
るため、通常は、粉末に担持させ樹脂系と混合する。The blending amount of maleic anhydride graft-polymerized in a mixture of linear low-density polyethylene and ethylene-ethylenically unsaturated group-containing ester copolymer or nonpolar polyolefin-based low crystalline resin is in the range of 0.05-5.0% by weight. And a particularly preferred range is 0.1-2.0% by weight. If the content of maleic anhydride is less than 0.05% by weight, the improvement in the adhesiveness is slight, while if it is more than 5.0% by weight, the improvement in the adhesive strength is not reached and gel formation is observed. Other properties are reduced. In order to carry out the graft polymerization reaction, if the temperature condition is appropriately selected, the polymerization reaction proceeds even in the absence of the radical initiator, but the presence thereof is preferable. Suitable radical initiators are dialkyl peroxides and peroxyketals. Since the added amount is very small, it is usually supported on powder and mixed with the resin system.

本発明に使用される導電材は、アセチレンブラツク、フ
アーネスブラツク、ケツチユンブラツク等のカーボンブ
ラツク及び／又はカーボン繊維及び／又は黒鉛及び／又
は金属粉末が使用できる。良導電性を要求される場合
は、当然導電材の添加量も多くなる。フイルム加工性を
考慮すると、粒子系が小さくかつ導電効率の高いカーボ
ンブラツク、中でもケツチエンブラツクを使う方が好ま
しい。As the conductive material used in the present invention, carbon black and / or carbon fiber and / or graphite and / or metal powder such as acetylene black, fannes black, and ketchyun black can be used. When good conductivity is required, the amount of conductive material added is naturally large. Considering the film processability, it is preferable to use a carbon black having a small particle size and a high electroconductivity, especially a ketene black.

被着体としては、アルミニウム、鉄、銅、亜鉛、スズ等
各種金属、ポリ塩化ビニール、ナイロン、ポリスチレ
ン、ポリエチレンテレフタレート等の各種プラスチツク
やガラス等の無機材が対象となり、高い接着力が得られ
る。As the adherend, various metals such as aluminum, iron, copper, zinc, tin, various plastics such as polyvinyl chloride, nylon, polystyrene, polyethylene terephthalate, and inorganic materials such as glass can be used, and high adhesion can be obtained.

〔実施例〕〔Example〕

ポリエチレン（表１中、樹脂Ａ）及び低温接着性の向
上、接着相乗効果・高充填性向上付与材としての素材
（表１中、樹脂Ｂ）の合計100重量部に対し、グラフト
重合モノマー及び同助剤をヘンシエルミキサーで均一に
分散混合し、押出機に供給する。スクリユー径55mm、L/
D＝28の２軸押出機を使用し、スクリユー回転数50rpm、
バレル温度を220℃と設定し、溶融状態でグラフト重合
反応生成物を得た（以下、耐熱接着性樹脂と称する）。Polyethylene (resin A in Table 1) and a graft polymerization monomer and 100 parts by weight of the material (resin B in Table 1) as a material for improving low-temperature adhesiveness, adhesion synergistic effect, and high filling property are added. The auxiliaries are uniformly dispersed and mixed with a Henschel mixer and fed to the extruder. Screen diameter 55 mm, L /
Using a twin-screw extruder with D = 28, screw speed 50 rpm,
The barrel temperature was set to 220 ° C., and a graft polymerization reaction product was obtained in a molten state (hereinafter referred to as heat resistant adhesive resin).

引き続き、表２に示すように得られた耐熱接着性樹脂10
0重量部に対し所定の導電材と少量の酸化安定剤及び分
散剤を70リツトルのバンバリーミキサーに投入し、温度
170-190℃、練時間５−８分で均一に溶融分散混練り
し、ロールでシート状にした後３−4mm角のペレツト状
に切断し、耐熱導電接着性樹脂組成物を得た。Subsequently, the heat-resistant adhesive resin 10 obtained as shown in Table 2 was used.
Charge 0 parts by weight of the specified conductive material and a small amount of oxidation stabilizer and dispersant into a 70-liter Banbury mixer, and
The mixture was uniformly melt-dispersed and kneaded at 170-190 ° C. for 5-8 minutes for kneading, formed into a sheet by a roll, and then cut into a pellet of 3-4 mm square to obtain a heat-resistant conductive adhesive resin composition.

ここで使用した素材について述べる。 The materials used here will be described.

（評価法） 試料作成 １） 被着体が金属（鉄、ステンレス、アルミニウム
等）の場合：アルミの場合は0.2mm厚、他は0.05-0.10mm
厚のシートを準備し、キシレン等で表面を洗浄した後、
試験に供する。 (Evaluation method) Sample preparation 1) When the adherend is a metal (iron, stainless steel, aluminum, etc.): 0.2 mm thickness for aluminum, 0.05-0.10 mm for others
After preparing a thick sheet and cleaning the surface with xylene etc.,
Provide for the test.

得られた、耐熱導電接着性樹脂を圧縮成形法で、0.5mm
のシートを作成する。引き続き、前記金属シートと180
℃、30kg/cm2加圧１分で貼合せ品を得る。キズを付けな
い様に注意深く10mm幅に切断し試験片とする。The heat-resistant conductive adhesive resin obtained was compressed by 0.5 mm.
Create a sheet of. Then, the metal sheet and 180
A bonded product is obtained at 30 ° C. and a pressure of 30 kg / cm 2 for 1 minute. Carefully cut into 10 mm width to make a test piece without scratches.

２） 被着体が樹脂や曲げることの困難なガラス等の無
機材の場合：樹脂の場合は圧縮成形法により2mm厚のシ
ートを作成する。一方、得られた耐熱導電接着性樹脂の
中で、可能なものに付いては、0.1mm厚のフイルムをイ
ンフレ法等で準備する。引き続き、被着体／耐熱導電接
着性樹脂フイルム／アルミニウムシートの構成で、180
℃、30kg/cm2加圧１分の条件で圧縮、貼合せ品を得る。
被着体とは、ガラスも含む。2) When the adherend is resin or an inorganic material such as glass that is difficult to bend: In the case of resin, a 2 mm thick sheet is prepared by compression molding. On the other hand, among the obtained heat-resistant conductive adhesive resins, 0.1 mm-thick films are prepared by the inflation method or the like for possible ones. Then, the structure of adherend / heat resistant conductive adhesive resin film / aluminum sheet
Compress at 30 ° C. and 30 kg / cm 2 pressure for 1 minute to obtain a bonded product.
The adherend also includes glass.

キズを付けないように注意深く、10mm幅にアルミニウム
と耐熱導電性接着樹脂フイルム相のみを切断し、試験片
とする。Carefully cut the aluminum and the heat-resistant conductive adhesive resin film phase to a width of 10 mm to make a test piece so as not to damage it.

剥離強さの測定 通常の引張試験機により100mm/分の速度で降伏点強さを
求め、180°剥離強さとする。Measurement of Peel Strength Determine the yield strength at a speed of 100 mm / min using a normal tensile tester to obtain 180 ° peel strength.

前記の２）即ち、曲げ強さの高い被着体の場合、剥離面
は被着体と耐熱導電接着性樹脂との間となる様注意して
行う。In the above 2), that is, in the case of an adherend having a high bending strength, care is taken so that the peeling surface is between the adherend and the heat resistant conductive adhesive resin.

（表中注） ＊ 耐熱導電接着性樹脂のフイルム化が困難の為、ずれ
剥離強さを測定。非常に高い値となり、比較データとし
て、使えないので記載省略。(Note in the table) * Since it is difficult to make a heat resistant conductive adhesive resin into a film, the shift peel strength is measured. The value is extremely high and cannot be used as comparison data, so the description is omitted.

＊＊ 耐熱導電接着性樹脂の素材破壊となる。値として
は、1.2-1.5kg/cm2以上。** The material of the heat resistant conductive adhesive resin is destroyed. The value is 1.2-1.5 kg / cm 2 or more.

１） 実施例４、３、２、１は直鎖状低密度ポリエチレ
ンをエチレン−エチルアクリレート共重合体の混合比を
変えることによる効果がみられる。直鎖状低密度ポリエ
チレン単体の場合よりもエチレン−エチルアクリレート
共重合体を混合することにより、耐熱性、耐温水性はや
ゝ低下するものの初期接着力及び低温接着性は向上し大
幅に改善される。しかし、直鎖状低密度ポリエチレン単
体でも（実施例４）、実際の使用上は総合的な品質バラ
ンス上非常に優れた特性を発揮する。比較例として高密
度ポリエチレン（比較例１）は低温接着性、成形加工性
に劣り、低密度ポリエチレン（比較例２）及びこれとエ
チレン−エチルアクリレート共重合体との混合系（比較
例３）は、初期接着力が低い。また、エチレン−エチル
アクリレート共重合体単体の場合は（比較例４）、それ
自体の強度が弱く、初期接着力はある水準に達している
が、剥離試験時に自己破壊を起こし、インフレフイルム
加工時にも膜が不安定となりブロツキング等の問題が起
こり易い。 1) Examples 4, 3, 2 and 1 show the effect of changing the mixing ratio of the linear low density polyethylene to the ethylene-ethyl acrylate copolymer. By mixing the ethylene-ethyl acrylate copolymer compared with the case of linear low density polyethylene alone, the heat resistance and hot water resistance are slightly reduced, but the initial adhesive strength and low temperature adhesiveness are improved and greatly improved. It However, even the linear low-density polyethylene alone (Example 4) exhibits extremely excellent properties in terms of overall quality balance in actual use. As a comparative example, high-density polyethylene (Comparative Example 1) is inferior in low-temperature adhesiveness and moldability, and low-density polyethylene (Comparative Example 2) and a mixed system of this and an ethylene-ethyl acrylate copolymer (Comparative Example 3) are , Initial adhesion is low. Further, in the case of the ethylene-ethyl acrylate copolymer alone (Comparative Example 4), the strength of itself was weak and the initial adhesive strength reached a certain level, but self-destruction occurred during the peeling test, and during the inflation film processing. Also, the film becomes unstable and problems such as blocking easily occur.

２） 実施例11に示すようにケツチエンブラツクECの濃
度を倍量に増加しても初期接着性を始め、耐久性の低下
は極めてわずかであり加工性もよく、比較例１、２及び
３に比べ優れている。2) As shown in Example 11, even if the concentration of Ketjen black EC was doubled, the initial adhesiveness started and the durability was extremely small and the workability was good, and Comparative Examples 1, 2 and 3 were used. Is superior to.

３） 同様に導電材の種類を替え、量も増加させても実
施例５及び６に見られるごとく、初期接着力の低下が見
られるものの、比較例１、２、３に比べ優れており、イ
ンフレフイルム加工も加能である。但し、カーボン繊維
の場合（実施例６）は厚物フイルム加工は可能である
が、薄肉化は困難である。実施例１、２、３の樹脂組成
においては、導電材の高充填能力が極めて優れており、
通常の低密度ポリエチレンや、高密度ポリエチレン等で
はエチレン−エステル共重合体との混合系であつても得
ることのできない特性である。3) Similarly, even if the kind of the conductive material is changed and the amount is increased, as shown in Examples 5 and 6, the initial adhesive strength is decreased, but it is superior to Comparative Examples 1, 2 and 3. Inflation film processing is also available. However, in the case of carbon fiber (Example 6), thick film processing is possible, but thinning is difficult. In the resin compositions of Examples 1, 2 and 3, the high filling capacity of the conductive material is extremely excellent,
It is a characteristic that ordinary low-density polyethylene, high-density polyethylene, and the like cannot be obtained even in a mixed system with an ethylene-ester copolymer.

４） 実施例７にエチレン−エステル共重合体として、
エチレン−酢酸ビニル共重合体を、同じく実施例８に無
極性ポリオレフイン系低結晶性樹脂に付いてのデータを
示す。また、無水マレイン酸のかわりにアクリル酸又は
不飽和エポキシ化合物の一種であるグリシジルメタクリ
レート（日本油脂工業製、ブレンマー−Ｇ）について検
討を行つた（実施例９、10）。いずれも他実施例と大き
な差は見られず、比較例に比べ優れた結果となつた。4) In Example 7, as an ethylene-ester copolymer,
Similarly, in Example 8, data of an ethylene-vinyl acetate copolymer attached to a nonpolar polyolefin low crystallinity resin is shown. Further, in place of maleic anhydride, acrylic acid or glycidyl methacrylate (Blenmer-G, manufactured by NOF CORPORATION), which is one of unsaturated epoxy compounds, was examined (Examples 9 and 10). No significant difference was observed with any of the other examples, and the results were superior to the comparative examples.

〔本発明の効果〕[Effect of the present invention]

本発明者らは、従来の低密度ポリエチレン或るいは高密
度ポリエチレンには見られない、低圧法低密度ポリエチ
レン、直鎖状低密度ポリエチレンを使用することによ
り、直鎖状低密度ポリエチレンとエチレン−エチレン性
不飽和基含有エステル共重合体又は無極性ポリオレフイ
ン系低結晶性樹脂の混合系に接着性及び導電性を付与
し、実用上問題となつていた次に示す諸問題点を解決
し、関連産業の進歩に寄与できたものと信ずる。即ち、
（１）各種基材に対し高い接着力を得た。（２）かつ高
い温度域まで高い接着力を維持し得る（接着耐熱性）。
（３）長期に渡つて高い接着力が維持される（接着耐久
性）。（４）比較的低温で接着が可能である（低温接着
性）。（５）加工性が容易でかつ得られた製品の品質特
性が高く維持される。等々をあげることができる。The present inventors have found that by using low-pressure process low-density polyethylene and linear low-density polyethylene, which are not found in conventional low-density polyethylene or high-density polyethylene, linear low-density polyethylene and ethylene- Adhesiveness and conductivity were added to a mixed system of an ethylenically unsaturated group-containing ester copolymer or a non-polar polyolefin type low crystalline resin, and the following problems that had been a problem in practical use were solved. We believe that it has contributed to the progress of industry. That is,
(1) A high adhesive strength was obtained for various base materials. (2) And high adhesive strength can be maintained up to a high temperature range (adhesion heat resistance).
(3) High adhesive strength is maintained over a long period of time (adhesion durability). (4) Adhesion is possible at a relatively low temperature (low temperature adhesion). (5) The workability is easy and the quality characteristics of the obtained product are maintained high. And so on.

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】（ａ） 下記の混合物： （ｉ） 不飽和有機酸類若しくはそれらの酸無水物、酸
ハロゲン化物、酸アミド若しくは酸イミドで又は不飽和
エポキシ化合物類でグラフト変性された直鎖状低密度ポ
リエチレンと不飽和有機酸類若しくはそれらの酸無水
物、酸ハロゲン化物、酸アミド若しくは酸イミドで又は
不飽和エポキシ化合物類でグラフト変性されたエチレン
−エチレン性不飽和基含有エステル共重合体との混合
物、及び （ii） 上記グラフト変性された直鎖状低密度ポリエチ
レンと不飽和有機酸類若しくはそれらの酸無水物、酸ハ
ロゲン化物、酸アミド若しくは酸イミドで又は不飽和エ
ポキシ化合物類でグラフト変性された無極性ポリオレフ
ィン系低結晶性樹脂との混合物 から選択されたグラフト変性物50〜95重量％と、 （ｂ） 粉末導電性物質50〜５重量％ とから成ることを特徴とする成形加工が容易でかつ低温
接着性に優れた耐熱導電性接着性樹脂組成物。1. (a) The following mixture: (i) a linear chain graft-modified with unsaturated organic acids or their acid anhydrides, acid halides, acid amides or acid imides or with unsaturated epoxy compounds. Of low-density polyethylene and unsaturated organic acids or their acid anhydrides, acid halides, acid amides or acid imides or ethylene-ethylenically unsaturated group-containing ester copolymers graft-modified with unsaturated epoxy compounds A mixture, and (ii) graft-modified linear low-density polyethylene with unsaturated organic acids or their acid anhydrides, acid halides, acid amides or acid imides, or with unsaturated epoxy compounds 50 to 95% by weight of a graft modified product selected from a mixture with a non-polar polyolefin low crystalline resin, and (b) powder Conductive material 50 to 5% by weight to consist easily molded, characterized in a and heat conductive adhesive resin composition having excellent low-temperature adhesiveness. 【請求項２】直鎖状低密度ポリエチレンが気相法によっ
て得られたものでメルトインデックスが0.5-50の範囲で
あることを特徴とする特許請求の範囲第１項記載の耐熱
導電性接着性樹脂組成物。2. The heat-resistant conductive adhesive according to claim 1, wherein the linear low-density polyethylene is obtained by a vapor phase method and has a melt index in the range of 0.5-50. Resin composition. 【請求項３】直鎖状低密度ポリエチレンが重量平均分子
量（Mw）と数平均分子量（Mn）との比（Mw）／（Mn）が
2.5-4.0であるような分子量分布を有することを特徴と
する特許請求の範囲第２項記載の耐熱導電性接着性樹脂
組成物。3. The linear low density polyethylene has a ratio (Mw) / (Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn).
The heat-resistant conductive adhesive resin composition according to claim 2, which has a molecular weight distribution of 2.5-4.0.
JP28890186A 1986-12-05 1986-12-05 Heat-resistant conductive adhesive resin composition Expired - Lifetime JPH0764962B2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP28890186A JPH0764962B2 (en) 1986-12-05 1986-12-05 Heat-resistant conductive adhesive resin composition
US07/353,598 US5176852A (en) 1986-12-05 1989-05-18 Adhesive compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP28890186A JPH0764962B2 (en) 1986-12-05 1986-12-05 Heat-resistant conductive adhesive resin composition

Publications (2)

Publication Number Publication Date
JPS63142050A JPS63142050A (en) 1988-06-14
JPH0764962B2 true JPH0764962B2 (en) 1995-07-12

Family

ID=17736249

Family Applications (1)

Application Number Title Priority Date Filing Date
JP28890186A Expired - Lifetime JPH0764962B2 (en) 1986-12-05 1986-12-05 Heat-resistant conductive adhesive resin composition

Country Status (2)

Country Link
US (1) US5176852A (en)
JP (1) JPH0764962B2 (en)

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ES2108282T3 (en) * 1992-06-02 1997-12-16 Alza Corp APPARATUS FOR THE IONTOPHORETICAL RELEASE OF PHARMACES.
GB9807198D0 (en) * 1998-04-04 1998-06-03 British Aerospace Adhesively bonded joints in carbon fibre composite structures
JP5458488B2 (en) * 2007-11-30 2014-04-02 東ソー株式会社 Conductive film, sputtering target using the same, and method for producing sputtering target
WO2010021899A1 (en) 2008-08-18 2010-02-25 Productive Research LLC. Formable light weight composites
EP2519376B1 (en) 2009-12-28 2020-11-25 Productive Research LLC. Process for welding composite materials and articles therefrom
US9415568B2 (en) 2010-02-15 2016-08-16 Productive Research Llc Formable light weight composite material systems and methods
CN101899275B (en) * 2010-07-15 2012-02-08 华东理工大学 Hot-melt adhesive for adhering with epoxy resin and preparation method thereof
JP5648720B2 (en) * 2013-07-09 2015-01-07 東ソー株式会社 Sputtering target using conductive film and method for producing the same
TWI632730B (en) * 2016-11-29 2018-08-11 天邁科技股份有限公司 Method of manufacturing waveguide assembly and structure thereof
US11338552B2 (en) 2019-02-15 2022-05-24 Productive Research Llc Composite materials, vehicle applications and methods thereof

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JPS5813585B2 (en) * 1974-01-17 1983-03-14 三井化学株式会社 Setup polyolefin inserts
JPS5714635A (en) * 1980-06-30 1982-01-25 Showa Denko Kk Polyolefin composition
JPS57177047A (en) * 1981-04-22 1982-10-30 Tokuyama Sekisui Kogyo Kk Electrically conductive resin composition and video disc record
JPS5853935A (en) * 1981-09-28 1983-03-30 Tokyo Ink Kk Electrically conductive and heat-weldable resin composition for plastic and metal
JPS5887142A (en) * 1981-11-20 1983-05-24 Showa Denko Kk Polyolefin composition
JPS59210966A (en) * 1983-05-16 1984-11-29 Daicel Chem Ind Ltd Highly conductive styrene resin composition
US4578286A (en) * 1984-02-08 1986-03-25 E. I. Du Pont De Nemours And Company Electrically conductive coating composition of a chlorosulfonated polyethylene
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Also Published As

Publication number Publication date
US5176852A (en) 1993-01-05
JPS63142050A (en) 1988-06-14

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